Benzohydroxamates

ABSTRACT

The compound having formula: (WHEREIN R represents an alkyl component of one through four carbon atoms, or alkenyl component of one through four carbon atoms, X represents hydrogen, methoxy or halogen and Y represents phenyl or phenyl substituted with methyl, chlorine or nitro) are prepared in accordance with the following equations: (WHEREIN R, X and Y

United States Patent Noguchi et al.

[451 Sept. 5, 1972 [54] BENZOI-IYDROXAMATES [72] Inventors: TeruhisaNoguchi, Fujisawa; Mitsuo Asada, I-liratsuka; Reiji Sakimoto, Takaoka;Koichi I-Iashimoto, Tsubatamachi, Kahoku-gun, all of Japan [73]Assignee: Nippon Soda Co., Ltd., Tokyo,

Japan 22 Filed: March 12, 1970 21 Appl. No.: 19,083

52] us. c|..... ..260/545 R, 424/315 [51] Int. Cl ..C07c 119/00 [58]Field of Search ..260/477, 471 R, 453, 545 R [56] References CitedUNITED STATES PATENTS 3,352,899 11/1967 Taneguche et al. ..224/2983,485,865 12/1969 Richter et al ..260/453 3,474,132 10/1969 Bernstein..260/453 3,444,232 5/1969 Berstein ..260/453 FOREIGN PATENTS ORAPPLICATIONS 979,562 l/1965 Great Britain ..260/477 1,221,280 2/ 1971Great Britain ..260/45 3 1,503,394 11/1967 France PrimaryExaminer-Lorraine A. Weinberger Assistant Examiner-R. S. WeissbergAttorney-George B. Oujevolk ABSTRACT (wherein R represents an alkylcomponent of one through four carbon atoms, or alkenyl component of onethrough four carbon atoms, X represents hydrogen, methoxy or halogen andY represents phenyl or phenyl substituted with methyl, chlorine ornitro) are prepared in accordance with the following equations:

OCH: X

base -CONIIOR ClCOY OCH:

C-C.Y CH3 ll (wherein R, X and Y represent the aforementionedcomponents) 2 Claims, No Drawings This invention relates to novelbenzohydroxamates and to a process for the preparation of the same.Further, the invention relates to acaricidal composition containing oneor more of said novel compounds.

Phytophagous mites furnish the greatest damage to plants and, in anorchard, a crop free from mite damage is scarcely found. Its damage isvery large and a large sum of money for extermination expense is spentannually. Further, some mites having resistance against the currentlyemployed acaricides have appeared recently. Therefore, it becomes amatter of importance to control the mites. Accordingly, development ofnovel, effective acaricides is desired in order to control these mites.

The inventors have discovered that application of the compounds of thisinvention, surprisingly, entirely protects or reduces damage to plantsdue to acarus species, especially Citrus red mite and European red mite,with a small amount and is free from phyto-toxicity.

The novel compounds of this invention are characterized by the followingformula:

wherein R represents alkyl of one through four carbon atoms,

or alkenyl of one through four carbon atoms,

X represents hydrogen, methoxy or halogen, and Y represents phenyl orphenyl substituted with methyl, chlorine or nitro.

The compounds of this invention have superior acaricidal and miteovicidal activity against mites such as Citrus red mite (Panonychuscitri McGregor), Desert spider mite (tetranychus desertorum Banks) andEuropean red mite (Panonychus ulmi Koch).

The compounds in this invention can be prepared in accordance with thefollowing equation.

OCHa X I base (III) @-ON110R ClCOY ocm X 1 N-O-R (wherein R, X and Yrepresent the aforesaid meanings) Usually the process of the inventionis carried out in a proper inert solvent at a temperature of about 20-l00 C. and the reaction terminates between 2 hours and hours.

In the case of using alkali metal hydroxide such as sodium and potassiumhydroxide as base (III) in the reaction, an inert solvent such asacetone, methyl ethylketone, chloroform, cyclohenanone, acetonitrile, ortetrahydrofuran is preferably employed at a temperature of about 200 C.Water has a tendency to decrease the yield of the products (IV), sogenerally one should be prepared to add, introduce or mix water to thereaction mixture. However if necessary, the minimum quantity of watermay be used. For example, in order to dissolve alkali metal hydroxide asmall portion of water may be added.

Furthermore a little amount of amino compounds such as triethyl aminecan be added as a catalyst.

After the reaction is terminated, the product (IV) are isolated from thereaction mixture by employing well known treatment. For example, in thecase of reaction in a water miscible solvent, after distilling thesolvent off under reduced pressure, the residue is dissolved in a non orlow polar solvent and aqueous sodium hydroxide solution. In case ofreaction in a non or low polar solvent, aqueous sodium hydroxidesolution is added into the reaction mixture. In both cases above, theprocedure is the same. The mixture consisting of a non or low polarsolvent containing the main product (IV) and aqueous sodium hydroxidesolution, is shaken. Unreacted starting materials and by-products oforganic acids are extracted into sodium hydroxide layer. Organic solventlayer is separated and dried; then the solvent is distilled ofi. Theproduct (IV) is obtained as crystals having high purity more thanpercent.

In order to facilitate a clear understanding of the invention, thefollowing preferred specific embodiment is described.

Example 1: Preparation of 01 OCHa N-OCaHs To a solution of 88.8g (3.42mole) ethyl 3 chloro 2,6 dimethoxy benzohydroxamate and 4.4g (0.0439mole) triethylamine in IL of chloroform and 34.2g (0.410 mole) of 40percent sodium hydroxide aqueous solution, 4.81 g (3.42 mole) benzoylchloride is added dropwise at 10 C. for about a half hour and themixture is stirred for two more hours at the same temperature.

After the termination of the reaction, the temperature is graduallyraised to room temperature. The water layer is separated and removed. Tothe organic solvent layer, 7g of 48 percent an aqueous solution ofsodium hydroxide is added and shaken to form a product in the waterlayer. A chloroform layer is dried and evaporated to obtain 115.6g ofcrystals. It was recrystalized from xylene to obtain g of pure crystalshaving melting point of 69l 1 1 C.

Some typical compounds of this invention are listed in Table 1 alongwith their property.

These typical compounds in Table l merely include some of the compoundsof this invention, so that the scope of this invention is not intendedto be limited only to those compounds listed in Table l.

cent, preferably l-60 weight percent, in Wettable powders, -70 weightpercent, preferably -50 weight percent, in emulsifiable concentrates,and 05-10 weight percent, preferably 'l-5 weight percent in dustformulations.

In the above formulation of the composition, auxiliary agents ormaterials, for example, inert mineral powders such as clay, talc,bentonite, vermuculite and diatomaceous earth, organic solvents such asethanol, benzene, xylene, kerosine, dimethylformamide anddimethylsulfoxide, dispersing agents such as sodium lignin sulfonate andcasein, and wetting agents such as alkylarylsulfonate, higher alcoholsulfate ester, alkyl aryl polyoxyethylene, alkylnaphthalene sulfonateand polyoxyethylene alkylphenol, may be employed according to the typeof the formulation for combating mites. Furthermore, the composition maybe applied as a mixture with other fungicides, insecticides, acaricides,plant growth regulators and fertilizers.

The non-limiting examples for the acaricidal compositions areillustrated as follows;

EXAMPLE 2 Wettable Powder Parts by Weight Compound I Higher alcoholsulfonate ester 5 Diatomaceous earth 75 These are mixed and micronizedin jet pulverizer to a particle size of 10-30 microns. in practical use,the micronized mixture is diluted to a concentration of 0.01 to 0.05percent of active ingredient with water. The suspension is applied asspray or drench.

TABLE 1-Continu0d No. of Melting compound Structural formula Chemicalname point C.)

13 ICl (|)CH3 N O C H Ethyl)-(-l-toluoyl)-3-cliloro-2,(i-(limothoxybcnzoliydroximatum .v -87 0-0-CH3 OCHa 14 7 Cl OCH; Allyl O-(l-toluoyl)-3-clilo1'o-2(i-(limothoxybonzoliydroximato til-60 I N 0 CHzCH CH 15 Cl OCH; AllylO-(i-toluoyl)-3-cl1loro-2 (hlimethoxyboilzohydroximute. 54-56 N 0 OH onCH 0c- CIIa 0cm ll Hereinafter, the compounds of this invention areEXAMPLE 3 represented by Compound No. in Table l. E l bl C t t In thisinvention, usually, a small but effective mu S1 13 e once m e amount ofthe compound is applied to plant surface by 25 Parts by Weight spraying,drenching or dusting to protect or control mites or rnite eggs. Theconcentrations of the active in- Compound 2 l0 gredients in theacarlcldal compositions of this mven- M y y y if y 5 tion vary accordingto type of formulation, and they g' 'zj 22 are, for example, used in arange of 5-80 weight per- 30 EXAMPLE 4 Dust Formulation Parts by WeightCompound 3 5 Talc 94.9 Alkylaryl polyoxyethylenc 0.1

These were mixed and crushed to fine powder. The dust formulation isusually applied as dusting powder at a rate of 3 to 5 kg. per are.

EXAMPLE 5 Mixed Wettable Powder Parts by Weight Compound 4 l5 Bis-(4-chlorophenyl)- methylcarbinol Higher alcohol sulfonate ester 4 Sodiumalkylnaphthalene sulfonate 2 l 3 Sodium lignin sulfonate Diatomaceousearth 6 These are mixed, micronized and applied following the procedureof Example 2.

in the Example 2-5, it is not intended to limit the emulsifying,wetting-or dispersing agents, carriers and solvents to the onesdescribed by way of illustration.

7 The compoundslisted in Table I possess very superiwherein R representsalkyl of one through four caror acaricidal activity compared to knowncompounds. bon atoms, or alkenyl of one through four carbon The superioracaricidal effect of the novel comatoms, X represents hydrogen, methoxyor pounds of this invention are clearly illustrated by the halogen and Yrepresents phenyl or phenyl subfollowing test. I stituted with methyl,chlorine or nitro. Test 1. Test for Control of Tetranychus mite 2. Acompound selected from the group consisting of About 30 adult femalemites of Tetranychus mite 00m Telranychus desertorum) laid on mainleaves of the -N u mm potted kidney bean plants grown 7 to days stage &O

after sprouting. One day later, the wounded mites are 10 O0 n i removedfrom the plants. The compounds to be tested 0 were sprayed on the plantsas water suspension con- 0 on taming 0.05% of the compound prepared bythe 1 N()C2Ils method of Example 2. After 3 days from spraying, adultmortality was counted, and then the surviving adult mites were removed.The viability of eggs deposited CH3 during this period was examinedafter 14 days from O spraying. 0 0 H3 Adult mortality and ovicidalactivity were calculated N OCZH5 by the following:

Adult mortality( ab)/a 100 (B O-C@Cl a: number ofliving mites inuntreated plots b: number of surviving mites in treated plots 0 Hovicidal activity (%)2 (a' b' )/a' X 100 C 3 N -O CII2CI'I=C]I3 a:number of eggs deposited b: number of hatched eggs O The rate of adultmortality or ovicidal activity was CH3 ([L recorded as follows:

Adult mortality or Ovicidal activity Rating 0 CH;

NOCHzCH=CH2 100% 30-99% 00-@0m 50-79% 0 0 Ha H 049% 0 c1 0 c H; Theresults are shown in Table 2. I

, o TABLE 2 O C C 1-1.

R 0 CH3 atln Compound No. 8 40 O I C1 01 Adult mortality ovicidal activty a N O CH3 1 2 -H-+ +4+ o o-@ 3 -H+ -H+ 0 0 I13 I] 4 +4-4- 0 2 i +.H Cl 0 C II: 7 I l No o2u 8 +H- 9 +0-4- 10 1 I H 0 0 11] 12 0 13 +-H- +1-1-Cl 0 o 11 1145 a N-OCzI-Is ,4,5 .4'-Tetrachloro- 1 d h r ip enylsul one(control') CH: O fi CH3 Note: Control is a commercial miticide. Cl 0 CH3N-o-otncn=cm From the foregoing evaluation date, it 1s apparent that thecompounds of this invention are effective acaro c rcide. 0 CH3 II Weclaim: 0

' LA compound represented by the formula 01 0 CH3

2. A compound selected from the group consisting of